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New ferrocenylalkylimidazolium salts [Fc(CH2)n(C3H3N2)R]X- were synthesised through the incorporation of green chemistry principles of atom economy and when feasible under solvent-free conditions. The products comprise a series of salts all characterised by the ferrocenyl moiety with variations in the length of the linker alkyl chain (n), the size of the imidazolium alkyl substituent (R) or the electronic nature of the counter-ion (X-). The dependence of the physical and electronic properties of the salts on the three main structural variants was studied. It was found that variation in the steric size of the R group has the most profound influence on the melting points of the ionic liquids. The compounds were fully characterised by IR, 1H and 13C NMR, MS and melting point determinations.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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A new chiral ferrocene-labelled tyrosine PNA monomer 1 has been synthesised in good yield in both racemic and enantiomerically pure forms. It is suitable for insertion in various positions of PNA oligomers, a possibility that has been preliminarily demonstrated by synthesising the dimer 16. Moreover, in view of possible applications to nucleic acid detection, a preliminary voltammetric investigation on the electrochemical activity of monomer 1 and its synthetic precursors has been carried out in DMF. It appears that, despite the bulkiness of the PNA monomer backbone, its insertion on the ferrocene group only moderately lowers the latter’s diffusion coefficients and peak currents, thus affording voltammetric detection limits in the order of 10-6-10 -7 M.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Cyclic voltammetry was used to create nonequilibrium populations of different solvation and configurational states of partially oxidized polyvinylferrocene (PVF). Oxidation levels were established by scanning either from a fully reduced state to the desired oxidation level or from a fully oxidized state to the desired level. Coulostatic conditions were then established by opening the external circuit, and subsequent mass and potential changes were followed. The film’s approach to equilibrium involves configurational changes within the polymer and simultaneous and subsequent solvent transfer. At very short times (t a¿¿ 0.2 s) the approach to equilibrium is limited by both solvation and reconfiguration processes. For a short time afterward (0.2 < t/s < 1.0) reconfiguration alone is rate limiting. At intermediate times (1 < t/s < 5) both processes play comparable roles. At long times (r > 5 s) solvation is the controlling step. The electroactive polymer film does not completely reach equilibrium even after 1 h at open circuit as evidenced by continuous small mass changes. These mass changes are the result of water transfer between the polymer film and the bathing electrolyte. A scheme of cubes model rationalizes mechanistic pathways leading to equilibrium. In particular, the observed extrema in mass (solvent population) are predicted. The electrode potential, after 1 h at open circuit, shows nearly Nernstian dependence on the redox composition for film states produced by either anodic or cathodic cyclic voltammetric scans. These Nernst plots are displaced by only a few millivolts because only a weak Nernstian dependence on film water content exists. Films that are 50% oxidized exhibit a sub-Nernstian response with respect to the perchlorate concentration in the bathing solution under permselective conditions.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Superbase-catalyzed (KOH/DMSO suspension as a catalyst) vinylation of hydroxymethyl- and hydroxyethylferrocenes with terminal and internal alkynes (acetylene, propyne, phenylacetylene, 3-ethynylpyridine, 1-propyn-1-yl-benzene, diphenylacetylene) affords hitherto unknown vinyl ethers of ferrocene in 30-93% yields depending on the alkyne structure and the tuneable ratio of reactants/KOH/DMSO. The vinylation smoothly proceeds under mild conditions (70-90 C, 0.25-13 h). With unsubstituted acetylene the process is readily realized under atmospheric pressure (yield of the corresponding vinyl ethers is 81-90%) though under pressure (initial pressure at room temperature is 10-13 atm, maximum pressure is 13-16 atm at the reaction temperature) the yield is close to quantitative (93%). The synthesized compounds were characterized using 1H and 13C NMR, and IR spectroscopy, as well as X-ray diffraction analysis.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Four new diferrocenyl hydrazone?enone compounds were obtained through a two-step reaction process involving 1,1?-diacetylferrocene, hydrazides, and ferrocenecarboxaldehyde. The structural characterization of two compounds, 6 and 7, through single-crystal X-ray diffraction showed the presence of a stable eclipsed conformation with the two ferrocenyl moieties oriented in trans geometries. The electrochemical and metal-ion sensing properties of the diferrocenyl-bifunctionalized compounds were explored to understand their potential in electronic communication and as receptor molecules. Compounds 1,1?-[(eta5-C5H5)Fe(eta5-C5H4)CH=CHC(O)(eta5-C5H4)Fe{(eta5-C5H4)C(CH3)=N?N(H)C(O)?R}] [R = C6H4OH (6), C6H4N-p (7)], showed selective interactions with Pb2+cations and distinct binding interactions with bovine serum albumin (BSA) protein. The mode of the metal?receptor interaction was established through DFT studies. The redox properties of the diferrocenyl compounds with variable end groups revealed distinct electronic communication between the two electroactive groups.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Alkenylferrocenes, FcCHCHCHCH2 have been synthesized from formylferrocene and allyl halides using beta-SnO and Pd(0) or Pt(II) as co-catalyst in organic aqueous medium. Monoallylated products have been isolated by similar reaction with 1,1?-bis-formylferrocene. These serve as potential precursors for multinuclear ferrocenophanes with extended conjugated ene-spacer.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Herein, we report the electrocatalytic voltammetry of holo and heme-free human sulfite oxidase (HSO) mediated by the synthetic iron complexes 1,2-bis(1,4,7-triaza-1-cyclononyl)ethane iron(III) bromide, ([Fe(dtne)]Br3.3H2O), potassium ferricyanide (K3[Fe(CN)6]), and ferrocene methanol (FM) at a 5-(4?-pyridinyl)-1,3,4-oxadiazole-2-thiol (Hpyt) modified gold working electrode. Holo HSO contains two electroactive redox cofactors, comprising a mostly negatively charged cyt b5 (heme) domain and a Mo cofactor (Moco) domain (the site of sulfite oxidation), where the surface near the active site is positively charged. We anticipated different catalytic voltammetry based on either repulsive or attractive electrostatic interactions between the holo or heme-free enzymes and the positively or negatively charged redox mediators. Both holo and heme-free HSO experimental catalytic voltammetry has been modeled by using electrochemical simulation across a range of sweep rates and concentrations of substrate and both positive and negatively charged electron acceptors ([Fe(dtne)]3+, [Fe(CN)6]3? and FM+), which provides new insights into the kinetics of the HSO catalytic mechanism. These mediator complexes have almost the same redox potential (all lying in the range +415 to +430 mV vs. NHE) and, thus, deliver the same driving force for electron transfer with the Mo cofactor. However, differences in the electrostatic affinities between HSO and the mediator have a significant influence on the electrocatalytic response.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Closely spaced 0.2-1 num, Au microelectrodes (50 num long, 1-2 num wide, and 0.1 num thick) on Si3N4 can be functionalized with poly (viniylferrocene), PVFc +/0, or with an N,N’-dibenzyl-4,4′-bipyridinium-based polymer, (BPQ2+/+)n’ derived from hydrolysis of N,N’-bis<(p-trimethoxysilyl)benzyl>-4,4′-bipyridinium (I).Two- or eight-microelectrode arrays have been functionalized with PVFc+/0 or (BPQ2+/+)n.Adjacent microelectrodes can be connected with either polymer in the sense that net current can pass from one microelectrode to another, through the polymer,when one electrode is held at a potential where the polymer is oxidized and the other electrode is held at a potential where the polymer is reduced.From such steady-state current an estimate of the diffusion coefficient for charge transport, DCT, in the polymer can be made; values in the range 10-9 – 10-10 cm2/s are found and accord well with earlier measurements of DCT for the polymers studied.A two-terminal diode can be fabricated by coating one electrode with (BPQ2+/+)n and an adjacent electrode with PVFc+/0 such that there is a connection between the microelectrodes via the (BPQ2+/+)n/PVFc+/0 contact.Current passes when the applied potential is such that the negative lead is attached to the (BPQ2+/+)n-coated electrode and the positive lead is attached to the PVFc+/0-coated electrode.When the applied potential approaches the difference in the Eo’s of the two polymers, current flows with the crucial feature being a downhill (by ca. 0.9 V) cross redox at the (BPQ2+/+)n/PVFc+/0) interface, BPQ+ + Fc+ –> BPQ2+ +Fc0.Current does not flow between the microelectrodes when the applied is in the opposite sense, because the reaction BPQ2+ + Fco –> BPQ+ + Fc+ is uphill by ca. 0.9 V.The switching time of a microelectrochemical diode is controlled by the time required to oxidize and reduce the polymers.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Electrical properties, such as charge propagation, dielectrics, surface potentials, conductivity, and piezoelectricity, play crucial roles in biomolecules, biomembranes, cells, tissues, and other biological samples. However, characterizing these electrical properties in delicate biosamples is challenging. Atomic Force Microscopy (AFM), the so called ?Lab on a Tip? is a powerful and multifunctional approach to quantitatively study the electrical properties of biological samples at the nanometer level. Herein, the principles, theories, and achievements of various modes of AFM in this area have been reviewed and summarized. Statement of Significance: Electrical properties such as dielectric and piezoelectric forces, charge propagation behaviors play important structural and functional roles in biosystems from the single molecule level, to cells and tissues. Atomic force microscopy (AFM) has emerged as an ideal toolkit to study electrical property of biology. Herein, the basic principles of AFM are described. We then discuss the multiple modes of AFM to study the electrical properties of biological samples, including Electrostatic Force Microscopy (EFM), Kelvin Probe Force Microscopy (KPFM), Conductive Atomic Force Microscopy (CAFM), Piezoresponse Force Microscopy (PFM) and Scanning ElectroChemical Microscopy (SECM). Finally, the outlook, prospects, and challenges of the various AFM modes when studying the electrical behaviour of the samples are discussed.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Scanning electrochemical microscopy (SECM) and copper staining are combined to achieve visualisation of proteins on surfaces. Proteins are adsorbed on a polyvinylidene fluoride (PVDF) membrane or on a polyethylene terephthalate (PET) surface and stained using a standard protocol involving copper salts. Salts are then reduced to copper and detected by SECM with ferrocene methanol as a redox mediator in aqueous solution. During the SECM scan, the potential is held at a value at which the oxidation of the redox mediator occurs and a positive feedback current is detected when scanning over copper clusters. A negative feedback is observed elsewhere. This method enables unspecific protein adsorption mapping on polymeric membranes and into microchannels without any requirement of enzymatic activity or affinity to a labelled secondary reporter.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion